The extraction behaviour of thorium(IV) from aqueous nitric acid employing 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) in the presence of tri-n-octyl phosphine oxide (TOPO) as well as tri-n-butyl phosphate (TBP) in xylene medium was investigated. The extraction constant (log k(ex)) for the binary organic phase species Th(PBI)(4) was determined to be 8.26 which is by far the largest amongst the corresponding values known for other beta-diketones. The overall extraction constant (log K) for the ternary species Th(PBI)(4) TBP and Th(PBI)(4).2TOPO were estimated to be 14.96 and 20.96 respectively. An inverse correlation of the adduct formation constant (log K(s)) with the pK(a) of the beta-diketones, 2-thenoyltrifluoroacetone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and HPBI, was observed. The steric as well as the electronic effects of adduct formation have been discussed. Analytical application of HPBI for the separation of (234)Th radiotracer from natural uranium (99.3% (238)U) has been suggested. 相似文献
Addition of lithiated methoxyallene to pivalonitrile afforded after aqueous workup the expected iminoallene 1 in excellent yield. Treatment of this intermediate with silver nitrate accomplished the desired cyclization to the electron-rich pyrrole derivative 2 in moderate yield. Surprisingly, trifluoroacetic acid converted iminoallene 1 to a mixture of enamide 3 and trifluoromethyl-substituted pyridinol 4 (together with its tautomer 5). A plausible mechanism proposed for this intriguing transformation involves addition of trifluoroacetate to the central allene carbon atom of an allenyl iminium intermediate as crucial step. Enamide 3 is converted to pyridinol 4 by an intramolecular aldol-type process. A practical direct synthesis of trifluoromethyl-substituted pyridinols 4, 10, 11, and 12 starting from typical nitriles and methoxyallene was established. Pyridinol 10 shows an interesting crystal packing with three molecules in the elementary cell and a remarkable helical supramolecular arrangement. Trifluoromethyl-substituted pyridinol 4 was converted to the corresponding pyridyl nonaflate 13, which is an excellent precursor for palladium-catalyzed reactions leading to pyridine derivatives 14-16 in good to excellent yields. The new synthesis of trifluoromethyl-substituted pyridines disclosed here demonstrates a novel reactivity pattern of lithiated methoxyallene which is incorporated into the products as the unusual tripolar synthon B. 相似文献
SAPO-5 molecular sieve was synthesized according to patent literature and characterized with X-ray diffraction, electron microscopy (SEM, TEM), and solid state magic angle spinning NMR spectroscopy. The material of particles in the micrometer region was found to consist of ca. 20 nm microcrystallites packed in mostly parallel orientation to ca. 200 nm sized agglomerates. The nitrogen adsorption isotherm was measured at 77.6 K over ca. 7 decades of pressure up to pore saturation. The course of the isotherm is interpreted to consist of filling of the nanopores (diameter, 0.73 nm) up to 2N(2)/unit cell, subsequent multilayer adsorption on the outer surface of the agglomerates, and, finally, pore condensation in the interparticle adsorption space. The nanopore adsorption can be quantitatively reproduced with the statistical mechanical model of a quasi one-dimensional lattice gas taking intermolecular interactions into account. The evaluated energy parameters are of physically reasonable magnitude and agree with literature data. The multilayer part of the adsorption isotherm can be well represented by the Brunauer-Emmett-Teller model yielding a specific outer space area (63 m(2) g(-)(1)) which is consistent with estimated geometrical and pore size analysis data. 相似文献
The effect of calcination temperature on the physico-chemical characterization of manganese nodule leached residue (MNLR) and water-washed manganese nodule leached residue (WMNLR) has been investigated on the basis of chemical analysis, XRD, TG-DTA, FTIR, surface hydroxyl groups, surface oxygen, reducing and oxidizing sites, surface area. XRD and IR confirm the presence of amorphous iron oxyhydroxides, delta-MnO2, which are converted to alpha-Fe2O3 and gamma-Mn2O3 phases above 400 degrees C of calcination, respectively. A solid solution of Fe2O3 and Mn2O3 is formed above 700 degrees C. The surface area, surface hydroxyl group, surface oxygen, reducing and oxidizing sites increase with the increase in calcination temperature up to 400 degrees C and then decrease with further rise in calcination temperature up to 700 degrees C. The catalytic activity of the sample towards H2O2 decomposition shows the similar trend as surface properties. A suitable Mn(3+)Mn4+ couple favours H2O2 decomposition reaction. The activity has been correlated with various physico-chemical properties. 相似文献
In the present paper, we report the standard molar Gibbs energy of formation for CaThF6 measured by gas equilibration and e.m.f. methods. The HF(g) vapour pressure over the equilibrium reaction: \({\text{CaThF}}_{6} \left( {\text{cr}} \right) + 2 {\text{H}}_{ 2} {\text{O}}\left( {\text{g}} \right) = {\text{CaF}}_{2} \left( {\text{cr}} \right) + {\text{ThO}}_{2} \left( {\text{cr}} \right) + 4{\text{HF}}\left( {\text{g}} \right)\) has been measured using transpiration technique. The above reaction mechanism has been established employing TG and XRD techniques. A fluoride e.m.f. cell: (−)Pt, CaF2(cr) + ThOF2(cr) + CaThF6(cr) |CaF2(cr)| NiO(cr) + NiF2(cr), Pt(+) has been constructed to measure Gibbs energy of formation of CaThF6 (cr) using CaF2 (cr) as a solid electrolyte. The isobaric heat capacity \({\text{Cp}}_{\text{m}}^{{\circ }} \left( T \right)\) of the compound has been measured using differential scanning calorimetric technique. Based on the experimental results, thermodynamic functions for CaThF6 have been generated.
The retention of 131I on ceramic rod coated with silver nitrate followed by coating with a polyurethane membrane to be applied in brachytherapy
was studied. The concentration of silver nitrate (20 g/l), the volume of 131I as a sodium iodide solution (100 μl), the pH of the reaction mixture (pH 9) etc., were optimized to get a maximum uptake
on the ceramic rod. The concentration of coating solution (5%, polyurethane in tetrahydrofuran) was also optimized to obtain
a minimum leaching of 131I activity in normal saline solution. After coating with a polyurethane membrane, the 131I absorbed on the ceramic rod exhibited low leachability (0.03%). This method can be applied for the preparation of 125I interstitial sources to be used in eye and prostate cancer therapy.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
A method for determination of anions and cations in boric acid is proposed by matrix volatilization. The boric acid matrix was eliminated as trimethyl borate ester in a vapour phase matrix elimination (VPME) system using a mixture of glycerol-methanol. In this VPME system, in situ reagent purification, sample decomposition and digest evaporation were achieved in a single step. Trace anions were separated on anion-exchange column (IonPac AS17) by an isocratic elution with 15 mM sodium hydroxide and the cations on a cation-exchange column (IonPac CS12) by 20 mM hydrochloric acid as eluents. Method detection limits (3sigma) for most ions ranged from 0.3 to 8 ng/g (ppb). Recovery experiments combined with comparison of data obtained by other methods were employed to verify the accuracy of the proposed method. Application of the method to determine trace levels of anions like acetate, oxalate, sulfate, phosphate and cations such as lithium, sodium, potassium, magnesium and calcium in two highly pure grades of boric acid using ion chromatography is demonstrated. 相似文献
The diacetylenic adducts, Fe2(CO)6{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe2(CO)6(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (1H, 13C, 77Se, and l25Te) spectroscopy. Trends in the chemical shifts of 77Se and 125Te NMR spectra of Fe2(CO)6{-EC(H) = C(C CMe)E} with a variation of EE are discussed. 相似文献